Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~ 7~ 2~
LIQUID DETERGENTS CONTAINING
BORIC ACID AND FORMATE TO STABILIZE ENZYMES
Roland G. Severson, Jr.
Technical Field
The present invention relates to heavy-duty liquid
detergents containing anionic synthetic surfactant, fatty
acid, water-soluble detergency builder, proteolytic
enzyme, boric acid or a boron compound capable of forming
boric acid in the composition, a water-soluble formate,
and calcium ion. The combination of boric acid and
formate has been found to provide improved protease
stability in the built, anionic-based compositions
herein.
The stabilization of enzymes is particularly diffi-
cult in built, heavy-duty liquid detergents containing
high levels of anionic surfactants and water. Anionic
surfactants, especially alkyl sulfates, tend to denature
enzymes and render them inactive. Detergent builders can
sequester the calcium ion needed for enzyme activity
and/or stability.
While many different enzyme stabilizers have been
proposed in the art, the combination of boric acid,
formate and calcium ion, preferably with a polyol,
provides unexpectedly good protease stability in the
present compositions.
Background Art
U.S. Patent 4,261,868, Hora et al, issued April 14,
1981, discloses liquid detergents containing as an
enzyme-stabilizing system, 2-25~ of a polyfunctional
amino compound selected from diethanolamine ! triethanol-
amine, di-isopropanolamine, triisopropanolamine and
tris(hydroxymethyl~ aminomethane, and 0.25-15~ of a boron
compound selected from boric acid, boric oxide, borax,
and sodium ortho-, meta- and pyroborate. The composi-
tions can contain 10-60% surfactant, including anionics,
and up to 40% build~r.
7~2~
-- 2 --
U.S. Patent 4,~04,115, Tai, issued September 13,
1983, discloses liquid cleaning compositions, preferably
built liquid detergents, containing enzyme, 1-15% alkali
metal pentaborate, 0-15% alkali metal sulfite, and 0-15%
of a polyol having 2~6 hydroxy groups. The compositions
can contain 1-60~ surfactant, preferably a mixture of
anionic and nonionic in a weight ratio of 6:1 to 1:1,
with or without soap. The compositions also preferably
contain 5-50~ builder.
Japanese Patent Application J78028515, assigned to
Nagase and Co., Ltd., published August 15, 1978, dis-
closes liquid detergents containing sorbitol and borax as
an enzyme-stabilizing system.
Canadian Patent 947,213, Dulat et al, issued May 14,
1974, discloses detergents containing enzymes and a mixed
phosphate/borate builder system. (This same technology
appears to be disclosed in U.S. Defensive Publication
T875,020, published June 23, 1970.)
Canadian Patent 1,092,036, Hora et al, issued
20 December 23, 1980, discloses enzymatic liquid detergents
containing 4-25~ polyol and boric acid (or boron-
equivalent) in a weight ratio of polyol to boric acid
less than 1. The compositions can contain 10-60% surfac-
tant and up to 40% builder, although they are preferably
unbuilt.
British Patent Application 2,079,305, Boskamp,
published January 20, 1982, discloses built liquid
detergents containing enzyme, 4-25% polyol, boric acid
(or boron-equivalent), in a weight ratio of polyol to
boric acid greater than 1, and 0.1-2~ of a neutralized
cross-linked polyacrylate. The compositions can contain
1-60% surfactant and up to 60% builder.
European Patent Application 80223, Boskamp, pub-
lished June 1, 1983, discloses li~uid detergents contain-
ing enzyme, 2-15% boric acid, 2-25% polyol or polyfunc-
tional amino compound, and 5-20% of a sulfur-based
reducing salt. The compositions can contain 1-60%
surfactant and up to 60% builder.
German Patent Application 3,330,323, published March
1, 1984, discloses in Examples 1 and 2 liquid detergents
containing anionic surfactant, enzyme, calcium and 2
sodium borate.
U.S. Patent 4,318,818, Letton et al, issued March 9,
1982, discloses liquid detergents containing an enzyme-
stabilizing system comprisin~ calcium ion and a low
molecular weight carboxylic acid or salt, preferably a
formate.
Summary of the Invention
This invention relates to heavy-duty liquid deter-
gent compositions comprising, by weight:
(a) from about 10% to about 50% of an anionic
~ synthetic surfactant;
(b) from about 3% to about 30% of a C10-C22 fatty
acid;
(c~ from about 2% to about 15% of a water-soluble
detergency builder; ~
(d~ from about 0.01% to about 5% of a proteolytic
enzyme;
(e) from about 0~25% to about 10% of boric acid or
a boron compound capable of forming boric acid in the
composition;
(f) from about 0.05% to about 5% of a water-soluble
formate;
(g) from about 1 to about 30 millimoles of calcium
ion per liter of composition; and
(h) from about 20% to about 80~ of water.
32~
q
Detailed Description of the Invention
The liquid detergents of the present invention
contain, as essential components, anionic synthetic
surfactant, fatty acid, water-soluble detergency builder,
proteolytic enzyme, boric acid or a boron compound
capable of forming boric acid in the composition, water-
soluble formate, calcium ion, and water. The combination
of boric acid and formate provides superior protease
stability in the built, anionic-based liquid detergents
lO herein. While not intending to be limited by theory, it
is believed that boric acid and calcium form
intramolecular bonds which effectively cross-link or
staple an enzyme molecule together, thereby holding it in
its active spatial conformation. Surprisingly, boric
15 acid appears to be a better enzyme stabilizer in the
present compositions than in compositions which are less
stressful to enzymes, such as those containing less
anionic surfactant and little or no builder. The
addition of a water-soluble formate further enhances
20 protease stability, although amylase stability appears to
be slightly less than that obtained using boric acid
alone.
Anionic Synthetic Surfactant
The compositions of the present invention contain
from about 10% to about 50~, preferably from about 12~ to
about 35%, and most preferably from about 15% to about
25~, by weight of an anionic synthetic surfactant.
Suitable anionic surfactants are disclosed in U.S. Patent
4,285,841, Barrat et al, issued August 25, 1981, and in
30 U.S. Patent 3,929,678, Laughlin et al, issued December
30, 1975. f
Useful anionic surfactants include the water-soluble
salts, particularly the alkali metal, ammonium and alkyl-
olammonium (e.g., monoethanolammonium or triethanolam-
35 monium) salts, of organic sulfuric reaction productshaving in their molecular structure an alkyl group
containing from about 10 to about 20 carbon atoms and a
sulfonic acid or sulfuric acid ester group. (Included in
the term "alkyl" is the alkyl portion of aryl groups.)
Examples of this group of synthetic surfactants are the
alkyl sulfates, especially those obtained by sulfating
the higher alcohols-(C8-Cl8 carbon atoms) such as those
produced by reducing the glycerides of tallow or coconut
oil; and the alkylbenzene sulfonates in which the alkyl
group contains from about 9 to about 15 carbon atoms, in
straight chain or branched chain configuration, e.g.,
those of the type described in U. S. Patents 2,220,099
-and 2,477,383. Especially valuable are linear straight
chain alkylbenzene sulfonates in which the average number
of carbon atoms in the alkyl group is from about 11 to
14.
Other anionic surfactants herein are the water-
soluble salts of: paraffin sulfonates containing from
about 8 to about 24 (preferably about 12 to 18) carbon
atoms; alkyl glyceryl ether sulfonates, especially those
ethers of C8 1~ alcohols (e.g., those derived from tallow
and coconut oil); alkyl phenol ethylene oxide ether
sulfates containing from about l to about 4 units of
ethylene oxide per molecule and from about 8 to about 12
carbon atoms in the alkyl group; and alkyl ethylene oxide
ether sulfates containing about l to about 4 units of
ethylene oxide per molecule and from about 10 to about 20
carbon atoms in the alkyl group.
Other useful anionic surfactants include the water-
soluble salts of esters of alpha-sulfonated fatty acids
containing from about 6 to 20 carbon atoms in the fatty
acid group and from about 1 to 10 carbon atoms in the
ester group; water-soluble salts of 2-acyloxy- alkane-l-
sulfonic acids containing from about 2 to 9 carbon atoms
in the acyl group and from about 9 to about 23 carbon
atoms in the alkane moiety; water-soluble salts of olefin
sulfonates containing from about 12 to 24 carbon atoms;
~Z 47 ~
- 6 -
and beka-alkyloxy alkane sulfonates containing from about
l to 3 carbon atoms in khe alkyl group and from abou~ 8
to 20 carbon atoms in the alkane moiety.
Preferred anionic surfactants are the C10-Cl8 alkyl
sulfates and alkyl ethoxy sulfates containing an average
of up to about 4 ethylene oxide units per mole of alkyl
sulfate, Cl1-C13 linear alkylbenzen~ sulfonates, and
mixtures thereof.
The compositions preferably contain from abouk 1~ to
about 5%, more preferably from about 2% to about 4%, by
weighk of unethoxylated alkyl sulfate. These alkyl
sulfates are desired for best detergency performance, but
are very denaturing to enzymes. Boric acid is believed
to be particularly effective at stabilizing enzymes in
such stressful compositions.
The compositions herein can optionally contain other
synthetic surfactants known in the art, such as the
nonionic t cationic, zwikterionic, and ampholytic surfac-
tants described in the above-cited Barrat et al and
Laughlin et al pat~nts.
A preferred cosurfactant/ used at a level of from
about 2% to about 25%, preferably from about 3% to about
15%, more preferably from about 4% to about 10%, by
weight of the composition, is an ethoxylated nonionic
surfactant of the formula R (OC2H4)nOH, wherein R1 is a
C10-Cl6 alkyl group or a C8-C12 alkyl phenyl group, n is
from about 3 to about 9, and said nonionic surfactant has
an HLB (hydrophile-lipophile balance) of from about 10 to
about 13. These surfactants are more fully described in
30 U.S. Patents 4,285,841, Barrat et al, issued August 25,
1981, and 4,284,532, Leikhim ek al, issued August 18,
1981 Particular-
ly preferred are condensation products of C12-C15 alco-
hols wikh from about 3 to about 8 moles of ethylene oxide
per mole of alcohol, e.g., Cl2-C13 alcohol condensed with
about 6.5 moles of ethylene~ oxide per mole of alcohol.
7~Z~i
Other preferred cosurfactants, used at a level of
from about 0.5% to about 3%, preferably from about 0.7
to about 2%, by weight are certain quaternary ammonium,
amine or amine oxide surfactants. The quaternary ammon-
S ium surfactants useful herein are of the formula:
[R (OR )y][R (OR )y]2R N Xwherein R is an alkyl or alkyl benzyl group having from
about 6 to about 16 carbon atoms in the alkyl chain; each
R is selected from the group consisting of -CH2CH2-,
-cH2cH(cH3)-~ -cH2cH(cH2oH)-~ -cH2cH2cH2-~ and miXtures
thereof; each R is selected from the group consisting of
Cl-C4 alkyl, C1-C4 hydroxyalkyl, benzyl, and hydrogen
when y is not 0; R is the same as R or is an alkyl
chain wherein the total number of carbon atoms of R2 plus
R5 is from about 8 to about 16; each y is from 0 to about
10 and the sum of the y values is from 0 to about 15; and
X is any compatible anion.
Preferred of the above are the alkyl quaternary
ammonium surfactants, especially the mono-long chain
alkyl surfactants described in the above formula when RS
is selected from the same groups as R . ~he most pre-
ferred quaternary ammonium surfactants are the chloride,
bromide and methylsulfate C8 ~6 alkyl trimethylammonium
salts, C8 16 alkyl di(hydroxyethyl)methylammonium salts,
the C8 16 alkyl hydroxyethyldimethylammonium salts, C8 16
alkyloxypropyl trimethylammonium salts, and the C8 16
alkyloxypropyl dihydroxyethylmethylammonium salts. Of
the above, the C10-C14 alkyl trimethylammonium salts are
preferred, e.g.,--decyl trimethylammonium methylsulfate~
lauryl trimethylammonium chloride, myristyl trimethyl-
ammonium bromide and coconut trimethylammonium chlorideand methylsulfate.
Under cold water washing conditions, i.e., less than
about 65F (18.3C), the C8 10 alkyl trimethylammonium
surfactants are particularly preferred since they have
lower Kraft boundaries and cxystallization temperatures
than the longer chain quaternary ammonium surfactants.
7~fZti
Amine surfactants useful herein are of the formula:
[R (OR )y][R (OR )y]R N
wherein the R , R , R , R and y substituents are as
defined above for the quaternary ammonium surfactants.
Particularly preferred are the Cl~_l6 alkyl dimethy
amines.
~ mine oxide surfactants useful herein are of the
formula:
[R (OR )y][R (OR )y]R N ~ 0
wherein the R , R , R , R and y substituents are also as
defined above for the quaternary ammonium surfactants.
PartiCularly preferred are the C12_16 alkyl dimethyl
amine oxides.
Amine and amine oxide surfactants are preferably
used at higher levels than the quaternary ammonium
surfactants since they typically are only partially
protonated in the present compositions. For example,
preferred compositions herein can contain from about 0.5%
to about 1.5% of the quaternary ammonium surfactant, or
from about 1~ to about 3% of the amine or amine oxide
surfactants.
Fatty Acid
The compositions of the present invention also
contain from about 3% to about 30%, more preferably from
about 5% to about 20%, most preferably from about 8~ to
about 15%, by weight of a fatty acid containing from
about 10 to about 22 carbon atoms. The fatty acid can
also contain from about 1 to about 10 ethylene oxide
units in the hydrocarbon chain. Preferred are saturated
fatty acids containing from about 10 to about 14 carbon
atoms. In addition, the weight ratio of C10-C12 fatty
acid to C14 fatty acid should be at least 1, preferably
at least 1.5.
~4'~2~
Sui~able saturated fatty acids can be obtained from
natural sources such as plant or animal esters ~e.g.,
stripped palm kernel oil, stripped palm oil and coconut
oil) or synthetically prepared te.g., via the oxidation
of petroleum or by hydrogenation of carbon monoxide via
the Fisher-Tropsch process). Examples of suitable
saturated fatty acids for use in the compositions of this
invention include capric, lauric, myristic, coconut and
palm kernel fatty acid. Preferred are saturated coconut
fatty acids, from about 5:1 to 1:1 (preferably about 3:1)
weight ratio mixtures of lauric and myristic acid,
mixtures of the above with minor amounts (e.g., 10~-30%
of total atty acid) of oleic acid; and stripped palm
kernel fatty acid.
~
The compositions herein contain from about 2% to
about 15%, preferably from about 3% to about 10%, more
preferably from about 4% to about 8%, by weight of a
water-soluble detergent builder material. Detergent
builders useful herein include the polycarboxylate,
polyphosphonate and polyphosphate builders described in
V.S. Patent 4t284,532, Leikhim et al, issued August 18,
1981. Polycarboxylate
builders are preferred.
Suitable polycarboxylate builders include the
various aminopolycarboxylates, cycloalkane polycarboxy-
lates, ether polycarboxylates, alkyl polycarboxylates,
epoxy polycarboxylates, tetrahydrofuran polycarboxylates,
benzene polyGarboxylates, and polyacetal polycarboxyl-
ates.
Examples of such polycarboxylate builders are sodium
and potassium ethylenediaminetetraacetate; sodium and
potassium nitrilotriacetate; the water-soluble salts of
phytic acid, e.g., sodium and potassium phytates, dis-
closed in U.S. Patent 1,739,942, Eckey, issued March 27,
~7~
-- 10 --
1956, the polycar-
boxylate materials described in U.S. Patent 3,364,103,
and the water-soluble
salts of polycarboxylate polymers and copolymers des-
cribed in U.S. Patent 3,308,067, Diehl, issued March 7,
1967.
Useful detergent builders also include the water-
soluble salts of polymeric aliphatic polycarboxylic acids
having the following structural and physical characteris-
tics: (a) a minimum molecular weight of about 350
calculated as to the acid form; (b) an equivalent weight
of about 50 to about 80 calculated as to acid form; (3)
at least 45 mole percent of the monomeric species having
at least two carboxyl radicals separated from each other
by not more than two carbon atoms: td~ the site ~f
attachment of the polymer chain of any carboxyl-
containing radical being separated by ~ot more than three
carbon atoms along the polymer chain from the site of
attachment of the next carboxyl-containing radical.
Specific examples of such ~uilders are the polymers and
copolymers of itaconic acid, aconitic acid, maleic acid,
mesaconic acid, fumaric acid, methylene malonic acid, and
citraconic acid.
Other suitable polycarboxylate builders include the
water-soluble salts, especially the sodium and potassium
salts, of mellitic acid, citric acid, pyromellitic acid,
benzene pentacarboxylic acid, oxydiacetic acid, carboxy-
methy;oxysuccinic acid, carboxymethyloxymalonic acid,
cis-cyclohexanehexacarboxylic acid, cis-cyclopentane-
tetracarboxylic acid and oxydisuccinic acid.
Other polycarboxylates for use herein are thepolyacetal carboxylates described in U.5. Patent
4,144,226, issued March 13, 1979 to Crutchfield et al,
and U.S. Patent 4,146,495, issued March 27, 1979 to
Crutchfield et alO
71~
11 --
Polypho~phonate builders u~eful herein are disclosed
in U.S. Patent 3,213,030, Diehl, issued October 19, 1965,
U.S. Patent 3,433,021, Roy, issued January 14, 1968, U.S.
Patent 3,292,1~1, Gedge, issued January 9, 1969 and U.S.
Patent 2,599,807, Bersworth, issued 3une 10, 1952
Preferred polyphos-
phonate builders are the sodium and potassium salts of
ethylene dipho5phonic acid, ethane l-hydroxy~ diphos-
phonic acid, and ethane-1,1,2-triphosphonic acid.
Preferred aminopolyphosphonate builders are the
sodium and potassium salts of diethylenetriaminepenta
methylenephosphonic acid, hexamethylenediaminetetra-
methylenephosphonic acid, diethylenediaminetetramethyl
enephosphonic acid, and nitrilotrimethylenephosphonic
acid.
Polyphosphates useful herein include the water-
soluble tripolyphosphates, pyrophosphates, and the
polymeric metaphosphates having a degree of polymeriza-
tion of from about 6 to 21. However, the tripolyphos-
phates and metaphosphates tend to hydrolyze to a mixtureof orthophosphate and pyrophosphate with prolonged
storage in aqueous solutions. Since the orthophosphates
precipitate but do not sequester water-hardness ions, the
pyrophosphates are the preferred polyphosphates for use
in the present invention. Particularly preferred is
potassium pyrophosphate since sodium pyrophosphate has a
tendency to precipitate from concentrated solutions at
low storage temperatures.
Citrates are highly preferred builder materials.
The compositions also preferably contain from about 0.1%
to abcut 1%, preferably from about 0.2% to about 0.6%, by
weight of a water-soluble salt of ethylenediamine tetra-
methylene phosphonic acid, diethylenetriamine penta-
methylenephosphonic acid, ethylenediamine tetraacetic
acid, or diethylenetriamine pentaacetic acid to enhance
cleaning performance when pretreating fabrics.
~,' , .
~24'7~
Proteolytic Enzyme
The compositions of the present invention contain
from about 0.01~ to about 5%, preferably from about 0.05%
to about 2%, by weight of the composition of a proteo-
lytic enzyme. Proteolytic enzymes are preferablyincluded in an amount sufficient to provide an activity
of from about 0.005 to about 0.1, more preferably from
about 0.01 to about 0.07, most preferably from about
0.012 to about 0.04, Anson units per ~ram of composition.
Suitable proteolytic enzymes include the many
species known to be adapted for use in detergent composi-
tions. Commercial enzyme preparations suc~h as "Alcalase"
sold by Novo Industries, and "Maxatase" sold by Gist-
Brocades, Delft, The Netherlands, are suitable. Other
preferred enzyme compositions include those comme~cially
available under the tradenames SP-72 ("Esperase") manu-
factured and sold by Novo~Industries, A/S, Copenhagen,
Denmark and "AZ-Protease" manufactured and sold by
Gist-Brocades, Delft, The Netherlands.
The proteases herein are preferably purified, prior
to incorporation in the finished compositlon, so that
~hey have no detectable odor at a concentration of less
than about 0.002 Anson units per gram in one liter of
distilled water. They preferably have no detectable odor
25 a~ a concentration of less than about 0.0025, more
preferably less than about 0.003, Anson units per gram
per liter of distilled water.
Proteases herein can be odor purified by any method
known in the art. Examples include the solvent pre-
cipitation methods described in Preci~itation of the
En~mes and Th 1r Stability in _High_ Alcohol _Concen-
trations by Bauer et al in the Israel J. Chem. 5(3),
pages 117-20 (1967) and Enzyme Preparations by Sugiura et
al and Yakusaigaku 1967, Volume 27(2), pages 135-9.
~L2~7~
- 13 -
Solvent initiated precipitation of a crude commer-
cial enzyme solution results in most of the enzymatic
activity being precipitated from solution and most of the
odor and color impurities remaining in the supernatant
liquid. Decantation or centrifugation of the supernatant
liquid from the precipitated enzyme results in an enzyme
fraction with enriched enzymatic activity/gram and
improved odor and color.
Various solvents or solvent pair combinations can be
used to effect the desired precipitation. For example,
methanol, ethanol, acetone, Other organic solvents, and
combinations of organic solvents with and without water
can be used. A highly preferred solvent is a co~bination
of water and 30-70% by weight ethanol. This appears to
be optimal to prevent enzyme deactivation and maximum
recovery of activity.
Purification of protease enzymes also pr~vide
benefits in the area of product color stability.
While the compositions can also conta~n amylases
known in the art, such~ as "Rapidase" sold by
Gist-srocades and "Termamyl" sold by Novo Indust--ies,
the addition of formate appears to decrease amylase
stability slightly from that obtained using boric a~id
alone. When present, amylases can be purified using
methods described above for purifying proteases to
provide some finished product odor and/or color benefits.
However, amylases are inherently less odorous and are
typically used at much lower levels than the proteases,
so malodors are generally not as severe.
A more complete disclosure of suitable enzymes can
be found in U.S. Patent 4,101,457, Place et al, issued
Jul~ 18, 1978.
Boric Acid
The compositions herein contain from about 0.25~ to
about 10%, preferably from about 0.5~ to about 5%, more
preferably from about 0.75~ to about 3%, by weight of
,,, y~
,;
~47~2~
- 14 -
boric acid or a compound capable of forming boric acid in
the composition (calculated on the basis of the boric
acid3. Boric acid is preferred, although other compounds
such as boric oxide, borax and other alkali metal borates
(e.g., sodium ortho-, meta- and pyroborate, and sodium
pentaborate) are suitable. Substituted boric acids
(e.g., phenylboronic acid, butane boronic acid, and
p-bromo phenylboronic acid) can also be used in place of
boric acid.
Water-Soluble Formate
The compositions also contain any of the water-
soluble formates described in U.S. Patent 4,318,818,
Letton et al, issued March 9, 1982.
Formate is presellt at a level of from
about 0.05% to about 5%, preferably from about 0.2% to
about 2%, most preferably from about 0.4% to about 1.5~,
by weight of the composition.
Calcium Ion
The composition also contains from about 1 to about
30, preferably from about 2 to about 20, more preferably
from about 5 to about 15, and most preferably from about
8 to about 12 millimoles of calcium ion per liter. The
level of calcium ion should be selected so that there is
always some minimum level available for the enzyme, after
allowing for complexation with builders, fatty acid,
etc., in the composition. Any water-soluble calcium salt
can be used as the source of calcium ion, including
calcium chloride, calcium formate, and calcium acetate.
A small amount of calcium ion, generally from about 0.05
to about 0.4 millimoles per liter, is often also present
in the composition due to calcium in the enzyme slurry
and formula water.
Water
Finally, the compositions herein contain from about
20% to about 80%, preferably from about 30% to about 60%,
more preferably from about 35% to about 50%, by weight of
water.
~7~2~
- 15 -
Optional Components
The compositions of the present invention can also
cvntain other materials known in the art to enhance
enzyme stability. Particularly preferred are polyols
containing only carbon, hydrogen and oxygen atoms. They
preferably contain from 2 to 6 carbon atoms and from 2 to
6 hydroxy groups. Examples include propylene glycol
(especially 1,2 propane diol, which is preferred),
ethylene glycol, glycerol, sorbitol, mannitol, and
glucose. The polyol generally represents from about 1%
to about 15~, preferably from about 1.5~ to about 10~,
most preferably from about 2~ to about 7~, by weight of
the composition. Preferably, the weight ratio of polyol
to boric acid is at least 1, more preferably at least
about 1.3.
The compositions herein have an initial pH of from
about 6.5 to about 10, preferably from about 7 to about
9, most preferably from about 7.5 to about 8.8, at a
concentration of 10~ by weight in water at 68F (20Cl.
Preferred pH buffers include monoethanolamine and tri-
ethanolamine. Monoethanolamine and triethanolamine also
further enhance enzyme stability, and preferably are
included at levels of from about 0.5% to about 10%,
preferably from about 1% to about 4%, by weight of the
COmposition-
Other optional components for use in the liquiddetergents herein include soil removal agents, antire-
deposition agents, suds regulants, hydrotropes, opaci-
fiers, antioxidants, bactericides, dyes, perfumes, and
brighteners known in the art. Such optional components
generally represent less than about 15~, preferably from
about 1% to about 10%, by weight of the composition.
The following examples illustrate the compositions
of the present invention.
All parts, percentages and ratios used herein are by
weight unless otherwise specifie~.
- 16 -
EXAMPLE I
The following compositions were prepared.
Component Wt. %
A B C D E
5 C13 linear alkylbenzene
sulfonic acid 7.2 7.2 7.2 7.2 7.2
C1~_15 alkyl polyethoxyl-
ate (2.25) sulfuric acid 10.8 10.8 10.8 10.8 10.8
(Cl4_l5 alkyl sulfuric
acid) (2.5) (2.5) (2.5) (2.5) (2.5)
C12-13 alcohol polyethoxyl-
ate (6.5)* 6.5 5.0 5.0 5.0 6.5
C12 alkyl trimethylammon-
ium chloride 1.2 0.6 0.6 - 0.6
15 C12 14 alkyl dimethyl
amine oxide - - - 2.5
C12-14 fatty acid 13.0 10.0 10.0 13.9 13.0
Oleic acid 2.0 - - 1.5 2.0
Citric acid (anhydrous) 4.0 4.0 4.0 4.0 4.0
Sodium diethylenetri-
amine pentaacetate 0.3 0.3 0.3 - 0.6
Sodium ethylenediamine
tetraacetate - - - 0.5
Protease enzyme (2.0 AU/g) 0.75 0.75 0.75 - -
25 Protease enzyme (1.5 AU/g) - - - 1.0 1.0
Amylase enzyme (325 Am. U/g) 0.16 0.16 0.16
Amylase enzyme (162 Am. U/g) - - - 0.37 0.37
15-18** 1.5 1.5 1.5 1.5 1.5
Monoethanolamine 2.0 - 1.0 - 2.3
30 Triethanolamine - 2.0 - 4.0 4.0
Sodium hydroxide 1.36 4.0 4.0
Potassium hydroxide 8.64 2.2 2.2
Sodium/potassium hydroxide - - - 2-4 3.4
1,2 Propane diol 6.25 2.5 2.5 8.0 4.0
35 Ethanol 7.75 7.0 8.0 5.5 6.5
. As indicated
Boric acld
P~$
Sodium formate As indicated
Calcium ion*** (mm/13 9.65 9.65 9.65 13.5 15.6
Minors and water Balance to 100
~ Alcohol and monoethoxylated alcohol removed.
** Tetraethylene pentaimine ethoxylated with 15-18 moles
(avg.) of ethylene oxide at each hydrogen site.
***Includes estimated 0.25 millimoles of calcium ion per
liter from enzyme slurry and formula water.
Enzyme stability in Composition A, as measured byO protease half-life at lOO~F (37.8C), was as follows. -
Al _A2 A3
% Boric acid - l.0 1.0
% Sodium formate 1.0 - 1.0
Half-life (weeks) 0.81 6.7 9.8
15 Enzyme stability in Composition A, as measured by
protease and amylase half-lives at 90F (32.2C), was as
follows.
A4 A5 A6 A7 A8 A9 A10 All
% Boric acid l.0 1.0 1.0 0.5 0.5 - - -
20 % Sodium formate - 0.5 1.0 0.51.0 1.0 1.5 2.0
Protease half-
life (weeks)* 17.3 38.2 66.4 19.7 12.4 9.5 9.7 9.1
Amylase half-
life (weeks) 15.3 14.1 13.3 10.8 9.3 5.5 5.2 5.8
*Half-lives should only be compared to others within this
test.
Enzyme stability in Composition B, as measured by
protease and amylase half-lives at 100F (37.8C), was as
follows.
B1 B2 B3 B4
% Boric acid - - 1.0 1.0
~ Sodium formate - 1.0 - 1.0
Protease half-life (weeks) 0.5 1.4 3.6 6.5
Amylase half-life (weeks) 3.5 4.7 17.1 17.1
2~
- 18 -
Enzyme stability in Composition C, as measured by
protease and amylase half-lives at 100F (37.8C), was as
follows.
C1 C2 C3 C4_
% Boric acid - 1.5 1.5 1.5
~ Sodium formate 1.O 1.0 - 0.12
Protease half-life (weeks) 1.0 12.4 6.4 5.4
Amylase half-life (weeks) 2.0 7.5 8.6 4.3
Enzyme stability in Compositions D and E, as meas--
10 ured by protease and amylase half-lives at 100F
(37.8C), was as follows. (NC means no significant
change in stability after six weeks.)
Dl D2 D3 D4 D5 D6
% Boric acid - 0.5 1.0 1.01.5 2.0
15 % Sodium formate 1.0 0.66 0.33 1.0
Protease half-life
(weeks) 5.6 8~7 11.814.5 16.7 17.0
Amylase half-life
(weeks) 40.5 63.2 NC NC NC NC
El E2 E3 E4 E5 E6
~ Boric acid - 0.5 1.0 1.0 1.5 2.0
% Sodium formate 1.0 0.66 0.33 1.0 - -
Protease half-life
(weeks) 8.9 11.1 14.617.2 33.4 21.7
Amylase half-life
(weeks) 15.8 21.0 37.6NC 38.6 NC
E7 E8E9 E10
% Boric acid 0 0 1 2
% Sodium formate 0 1 0 0
30 Protease half-life (weeks) 3.7 8.2 19.2 NC
Amylase half-life (weeks) 12.6 18.1 NC NC
The above results demonstrate that boric acid is a
much better enzyme stabilizer than sodium formate in
Compositions A-E of the invention. In addition, the
combination of boric acid and formate provides even
greater protease stability, but slightly less amylase
stability, than that obtained using boric acid alone.
~7(~2~
-- 19 --
The use of boric acid to stabilize enzymes in
Compositions A-E in place of sodium formate also allows
for a reduction in the level of sodium and calcium ions,
which enhances the stability of the compositions against
precipitation when stored at low temperatures or
underfreeze-thaw conditions.
EXAMPLE II
The following compositions were prepared.
Wt. %
10 mponent A B
Sodium C12_14 alcohol poly-
ethoxylate (3) sulfate 11.6
C12 13 alcohol polyethxylate (6.5) 21.5
C14 15 alcohol polyethoxylate t7)* - 18.0
15 C12 1~ alkyldimethyl amine oxide - 1.0
Ditallow dimethylammonium chloride - 3.0
TEPA ~ E15-18 1.5
Ethanol 10.0 7O5
Protease enzyme (2.0 AU/g) 1.3 0.75
20 Amylase enzyme (375 Am. U/g~ ~ 0.17
Boric acid As indicated
Sodium formate As indicated
Calcium ion*** (mm/l) 0.25 2.5
Minors and water Balance to 100
* Alcohol and monoethoxylated alcohol removed.
** Tetraethylene pentaimine ethoxylated with 15-18 moles
(avg.) of ethylene oxide at each hydrogen site.
*** Includes estimated 0.25 millimoles of calcium ion per
liter from enzyme slurry and formula water.
Enzyme stability in Compositions A and B, as meas-
ured by half-lives at 100F (37.8C), was as follows.
7~Z~i
- 20 -
A1 A2 A3 A4 A5 A5
% Boric acid - - 1.0 1.0 1.0
% Sodium formate - O.5 1.O - O.5 1.0
Protease half-life
iweeks) 3.0 7.4 7.4 2.6 2.7 3.0
Bl B2
~ Boric acid - 1.0
% Sodium formate 1.2
Protease half-life tweeks) 5.8 3.6
10 Amylase half-life (weeks) 10.3 8.8
These results demonstrate that sodium formate is a
better enzyme stabilizer in Compositions A and B (not
compositions within the scope of the invention) than is
boric acid. Furthermore, the addition of 1% boric acid
to Compositions Al, A2 and A3 tas in A4, A5, and A6~
reduces protease stability to less than or equal to that
obtained without formate in control Composition A1.
WE~T IS CLAIMED IS:
